Cellulosic composition of matter containing acetoxime



July 7, 1931. s. .1. CARROLL 1 CELLULOSIC COMPOSITION OF MATTER CONTAINING ACETOXIME Filed Aug. 50. 1929 /o 2o so 40 50 PLAsTmzER.

gnvcntoz EEQWEIL LT- Ea'rTmU Patented July 7, 1931 OPEC STEWART J. CARROLL, OF ROCHESTER, NEW YORK, ASSIGNOR TO EASTMAN KODAK COMPANY, OF ROCHESTER, NEW YORK, A. CORPORATION OF NEW YORK CELLULOSIC COMPOSITION OF MATTER CONTAINING AGETOXIME Application filed August 30, 1929.

This invention relates to compositions of matter in whlch cellulose derivatives, such as cellulose acetate, cellulose nitrate or cellulose ether, are combined or mixed with other substances, such as a compatible plasticizer, and a common solvent for both, with or without other useful addition agents, so that the resulting product will have properties such as will make the composition highly advantageous for use in the plastic and analogous arts, such, for instance, as the manufacture of wrapping sheets, photographic film, artificial silk, varnishes or lacquers, and the like. One object of this invention is. to produce a composition of matter which may be made into permanently transparent, strong and flexible-sheets or films of desired thinness duce a composition which will not injure, or

be injured by, the substances or surfaces with which it is associated during manufacture,

storage or use. Other and further objects will hereinafter become apparent to those skilled in the ar't'to which this invention pertains.

While cellulose acetates, nitrates and ethers have been known for decades it has also been known that to utilize them in the various plastic arts it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose of reducing the inflammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Simi- V larly addition compounds of various kinds have been employed to increase fiex1b1l1ty, transparency, toughness and other properties which will enhance the value of the resulting Serial No. 389,448.

addition agents a matter of considerable importance to the art.

I have discovered that valuable properties may be induced in and/or contributed to compositions containing cellulose derivatives, such'as cellulose acetate, by adding thereto the plasticizing compound acetoxime in the presence of a solvent, such as acetone, which will dissolve both the cellulose derivative and plasticizer. This plasticizer is a solid at ordinary atmospheric temperature and has the structural formula of o='No1a.

Itis compatible with cellulose derivatives and particularly compatible with cellulose acetate in the percentages hereinafter given. It is not an expensive compound and not particularly difficult to produce, or obtain upon the open market. The particularly useful properties which it induces in or contributes to a cellulosic composition containing it are hereinafter enumerated.

In order that those skilled in this art may better understand my invention I would state, r

by way of illustration, that for the manufacture of photographic film or other sheets my new composition of matter may be com pounded as follows: 100 parts of acetone soluble cellulose acetate i. e. cellulose acetate containing from 36% to 42% acetyl radical, approximately, is dissolved with stirring at atmospherictemperature in 300 to 500 parts,

preferably 400 parts, by weight, of acetone.

To this solution may be added from 10 to 50 Addition products for the same parts by weight, of acetoxime, it being found preferable to employ approximately 10 parts thereof. Within the limits stated, the amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which this plasticizer contributes to the finished product. The amount of solvent employed may also be decreased or increased, depending upon Whether it is desired to have a more or less freely flowing composition, respectively.

A composition of matter prepared as above described may be deposited upon any suitable film forming surface to form a film or sheet, as is well known to those skilled in the art. A film so produced has permanently brilliant transparency and low inflammability, burning no more readily than ordinary newsprint. Such film is tough and flexible as shown by the fact that it will with stand many folds upon a modified Schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for 149 days to air maintained at a temperature of C. the film still maintains flexibility, demonstrating that the film will withstand ordinary usage satisfactorily for many years, whereas a film formed from a mere solution of cellulose acetate in acetone or other similar solvent is brittle and fragile after being subjected to the same treatment for as little as thirty days or even a lesser time. The sum total of the above advantageous properties of aprodnot produced from my new compos1t1on is considerably in excess of that of products produced with what have previously been regarded as the better plasticizers.

Other smilar solvents (instead of acetone) which are compatible with the cellulose acetate and my new plasticizer may also occur to those skilled in this art. In like manner this plasticizer may be compounded with other single organic esters of cellulose, such 7 as cellulose propionate, butyrate and the like, or with mixed organic and/or inorganic esters, such as cellulose aceto-stearate, acetomalate, or cellulose nitro-acetate, or with the cellulose ethers, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

The accompanying drawing forming a part of this application, clearly illustrates the particular advantages of employing my novel plasticizer in the plastic arts. In this drawing there are plotted lines or curves graphically depicting the properties of film produced from a composition containing cellulose acetate and this plasticizer. On the horizontal axis is indicated the various percentages of my plasticizer that may be employed with the cellulosic derivative, this percentage being given in parts added to the cellulose derivative rather than parts of the composition;

for instance, 30 parts plasticizer added to 100 parts cellulose acetate is denoted as 30% plasticizer added. On the vertical axis at (a), on the left, is indicated in percentage over the check sample the initial flexibility of a film which has been formed as described from my novel composition and which has been subjected to air at 50 C. for 24 hours to free it of solvent; the rate of combustion of that film is also indicated by this same column (a) at (b) on the right is indicated the length of time in days that the film will main tain flexibility when subjected to air kept at a temperature of 65 C. The curve (A) depicts initial flexibility of the film, the curve (B) depicts the ability of the film to maintain flexibility and the curve (C) depicts the rate of combustion of the film-all with various percentages of my novel plasticizer and all as compared to the respective properties of a film produced from a solution of cellulose acetate in acetone and a hypothetical inert material substituted for the plasticizer as de noted by curve (D) indicating unity of 100% and 30 days for (a) and (b). be noted that my novel plasticizer has the faculty of giving, to a product produced therefrom, good initial flexibility and a low combustion rate, and that the product maintains its flexibility quite well. percentage of my plasticizer which it is desirable to employ to contribute any particular property to the final product will be obvious from an inspection of this drawing; the

best percentage to employ will depend upon;

which property it is desired to feature most in the final product.

Inasmuch as my above described composition of matter is quite useful in the production of films and sheets it will be apparent that my new plasticizer may also be employed with advantage in the other branches of the plastic art. For instance, my above described composition of matter may be employed in the manufacture of artificial silk by the dry spinning method. With the proper coagulating bath it may also be employed for wet spinning. ploy a composition of different viscosity or evaporation characteristics but this is a mere matter of changing the solvent proportion or adding evaporation retardants such as triacetin or other high or intermediate boiling constituents, as has been well known in the art for more than a decade. My novel plasticizer may also be employed with advantage in connection with a number of the known lacquer and varnish formulae with which it may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative solution and if non-solvents are added for the purpose of cheapening the composition they are added only to such an extent as will not precipitate the derivative from solution.

It will thus The preferred;

It may be desired to em-' Other uses Within the scope of my invention will also suggest themselves to those skilled in the art.

What I claim as my invention, and desire to be secured by Letters Patent of the United States, is:

1. A composition of matter comprising a cellulose derivative and acetoxime.

2. A composition of matter comprising cellulose acetate and acetoxime.

8. A composition of matter comprising 100 parts cellulose acetate and from about 10 to 50 parts, by Weight, of acetoxime.

4. A composition of matter comprising 100 parts of cellulose acetate and approximately 10 parts, by Weight, of acetoxime.

Signed at Rochester, N. Y. this 27th day of August, 1929.

STEWART J. CARROLL. 

